O-(methyl or ethyl)-O(S) lower alkyl-O-(4-phenoxyphenyl)phosphates

ABSTRACT

1. A COMPOUND OF THE FORMULA   1-(((R4)M-PHENYL)-O-),4-(R1-Y-P(=X)(-O-R2)-O-),(R3)N-   BENZENE   WHEREIN R1 REPRESENTS ALKYL WITH 1 TO 7 CARBON ATOMS, R2 REPRESENTS METHYL OR ETHYL, R3 AND R4 EACH REPRESENTS HYDROGEN, NITRO OR HALOGEN, M = 1 TO 5 AND N = 1 TO 4, AND X AND Y EACH REPRESENTS OXYGEN OR SULPHUR.

United States Patent Kristiansen Dec. 16, 1975 [75] Inventor: Odd Kristiansen, Mohlin,

Switzerland [73] Assignee: Ciba Geigy Corporation, Ardsley,

[22] Filed: May 6, 1974 [21] Appl. No.: 466,923

[30] Foreign Application Priority Data May 11, 1973 Switzerland 6721/73 [52] US. Cl 260/951; 424/217 [51] Int. Cl? C07F 9/165; AOlN 9/36 [58] Field of Search 260/951 [56] References Cited V UNITED STATES PATENTS 3,280,227 10/1966 Mitchell et a1 260/951 3.833.691 9/1974 Rathgeb 260/951 Primary ExaminerAnton H. Sutto Attorney, Agent, or Firm-Frederick H. Rabin [5 7] ABSTRACT NEW ESTERS Phosphorus compounds of the formula x 11 YR o M, O-P 1 wherein R represents'alkyl with l to 7 carbon atoms, R represents methyl or ethyl, R and R each representshydrogen, nitro or halogen, m 1 to 5 n l to 4, and X and Y each represents oxygen or sulphur, processes fortheir manufacture, and a method of using them in pest control.

15 Claims, No Drawings O-(METHYL OR ETHYL)-O( S) LOWER ALKYL-O-( 4-PHENOXYPHENYL )PHOSPHATES wherein R represents alkyl with l to 7 carbon atoms, R represents methyl or ethyl, R and R each repre- P-Cl Cl. (R

sents hydrogen, nitro or halogen, m l to 5 and n l to 4. and X and Y each represents oxygen or sulphur.

Halogen is to be understood as meaning fluorine, chlorine, bromine and/or iodine. preferably chlorine and/or bromine.

The alkyl groups represented by R can be straightchain or branched. Examples of such groups include: methyl, ethyl, n-butyl, iso-butyl, sec. butyl and tert. butyl, n-pentyl. n-hexyl. n-heptyl and isomers thereof Preferred compounds on account of their action are those of the formula I wherein R represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. butyl, n-pentyl or n-heptyl. R represents ethyl, R and R, each represents hydrogen, chlorine, bromine and/or nitro, m and n are each 1 or 2, X represents oxygen or sulphur and Y represents sulphur.

The compounds of the formula I can be manufactured by the following methods which are known per acid acceptor HOO'WQ v (R (Rp (III) MeO-Q'OQ 9 I acld acceptor (III) HYR acid acceptor E (IIIa) NeYRi I In the formulae II to IV, the'symbols R; to Ram and n-and X and Y have the same meanings as for the formula I and Me represents an alkali metal. in particular sodium or potassium. or represents the group (R);,N H. wherein R represents hydrogen or alkyl with l to 4 carbon atoms.

Suitable acid acceptors are: tertiary amines, e.g.. trialkylamines. pyridine. dialkyl anilines; inorganic bases, e.g., hydrides, hydroxides, carbonates and bicarbonates of alkali metals and alkaline earth metals. It is sometimes necessary to use catalysts in the reactions, e.g., copper or copper chloride. Processes la, 11: and 2 are carried out at a reaction temperature between -2C and +130C, at normal pressure. and in solvents or diluents.

Examples suitable solvents ordiluents are: ethers and ethereal compounds, e.g., diethyl ether, dipropyl ether. dioxane. tetrahydrofuran; amides, e.g. N,N-dialkylated carboxy amides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene. xylene. chloroform. chlorobenzene; nitriles, e.g.. acetonitrile; dimethyl sulphoxide. ketones, e.g., acetone, methyl ethyl ketone; water.

The starting materials of the formulae II, III.,IV and V are known and canbe manufactured in analogous manner to known methods. I

The compounds of the formula 1 exhibit a broad biocidal activity and can be used for the control of a variety of plant and animal pests.

In particular they are suitable for combating insects of the families:

Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae. Cimicidae, Phyrrhocoridae, Reduviidae,

Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelisae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, -Tenebrionidae, vCurulionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae. Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae as well as Acaridae of the families: Ixodidae, Argasidae, Tetranchidae, Dermanyssidae.

By addition of other insecticides and/or acaricides it is possible to improve substantially the insecticidal or acaricidal action and to adapt it to given circumstances.

Examples of suitable additives are: organic phosphorus compounds, nitrophenols and derivatives thereof; formamidines;. ureas; carbamatesand chlorinated hydrocarbons.

In addition to the above mentioned properties, the compounds of the formula I are also active against representatives of the division Thallophyta. Thus a number of these compounds exhibit bactericidal action. But they are active chiefly against fungi, especially against phytopathogenic fungi belonging to the following classes: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes.

The compounds of the formula I also exhibit a fungitoxic action against fungi which attack the plants from the soil.'The-new active substances are also suitable for treating seeds, fruit, tubers etc. from attack by fungus infections. The compounds of the formula I are also suitable for combating phytopathogenic nematodes.

The compounds of the formula I may be used as pure active substance or together with suitable carriers and- /or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in formulation technology. for exam- 4 ple natural or regenerated-substances. solvents. dispersants. wetting agents. adhesives, thickeners. binders and/or fertilisers.

For application. the compounds of the formula I may be processed to dusts, emulsion concentrates, granules, dispersions, sprays, to solutions or suspensions, in the conventional formulation which is commonly employed in application technology. Mention is also to be made of cattle dips and spray races, in which aqueous preparations are used.

The agents according to the invention are manufactured in known manner by intimately mixing and/0r grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances can take, and be used in, the following forms: Solid forms:

dusts, tracking agents,granules, coated granules,

impregnated granules and homogeneous granules.

Liquid forms:

a. active substances which are dispersible in water:

wettable powders, pasts, emulsions:

b. solutions.

The content of active substance in the above described agents is between 0.1 to in which connection it should be mentioned that, in the case of application from aircraft or some other suitable means of application. it is possible to use concentrations of up to 99.5% or even pure active substance.

The active substances of the formula I can, for example, be formulated as follows:

DUSTS The following substances are used to manufacture a. a 5% and b) a 2% dust: a. 5 parts of active substance 95 parts of talcum b. 2 parts of active substance 1 part of highly disperse silicic acid 97 parts of talcum. The active substances are mixed with the carriers and ground.

GRANULES The following substances are used to produce 5% granules:

5 parts of active substance,

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol,

91 parts of kaolin (particle size O.30.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The resulting solution is sprayed on kaolin, and the acetone is subsequently evaporated in vacuo.

WE'ITABLE POWDER The following constituents are used for the preparation of a) a 40%, b) and c) a 25%, and d) a 10% wettable powder:

a. 40'parts of active substance, 5 parts of sodium lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicic acid.

b. 25 parts of active substance, 4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk- /hydroxyethyl cellulose mixture 1:1), 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acid. 19.5 parts of Champagne chalk, 28.1 parts of kaolin.

c. 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture 1:1 8.3 parts 'of sodium aluminium silicate. 16.6 parts of kieselguhr, 46 parts of kaolin. d. parts of active substance, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, 5 parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with the additives. the mixture being then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.

EMULSIFIABLE CONCENTRATES The following substances are used to produce a) a 10% and b) a emulsifiable concentrate:

a. 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, 13.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylaryl sulphonate calcium salt, parts of dimethylformamide, 43.2 parts of xylene, 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, 10 parts of an alkylarylsulphonatelfatty alcoholglycol ether mixture, 5 parts of dimethylformamide. 57.5 parts of xylene.

From these concentrates it is possible to produce, by

dilution with water, emulsions of any desired concentration.

SPRAY The following constituents are used to prepared a 5% spray:

5 parts of active substance, 1 part of epichlorohydrin, 94 parts of benzene (boiling limits lCl90C).

EXAMPLE 1 With stirring. 41 g of O-ethyl-S-n-propylthiolphosphoric chloride in 60 ml of diethyl ether is added dropwise so rapidly to a solution. cooled to 10C, of 37 g of 4-hydroxydiphenyl'ether and 22 g of triethylamine in 500 ml of absolute diethyl ether that the temperature does not rise above 30C. The reaction mixture is stirred for a further 2 hours at 20-30C and treated. with continued stirring. with 300 ml of ice water. The organic phase is isolated, shaken once with water and twice with ice cold 5% sodium hydroxide solution and then washed neutral with water.

The ethereal phase is treated with activated charcoal, filtered, dried. and the solvent is evaporated off. The oily residue is dried for 3 hours at 70C and 0.1 Torr to yield the compound of the formula 0 ll OC H EXAMPLE 2 A. Insecticidal ingest poison action Cotton and potato plants were sprayed with a 0.05% aqueous emulsion (obtained from a 10% emulsifiable concentrate). After the coating had dried. the cotton plants were populated with Spodoptera' litloralis or Heliothis virescens larvae L and the potato plants with Heliothis virescens larvae L and the potato plants with Colorado potato bettle larvae (Leptinotarsa decemlineata). The test was carried out at 24C and 60% relative humidity. In the above test, the compounds according to Example 1 displayed good ingest poison action against Spodoptera littoralis. Heliothis and Leptinotarsa decemlineala larvae. i

B. System insecticidal action To determine the systemic action, rooted bean plants (Vicia fabae) were put into a 0.01% aqueous active substance solution (obtained from a emulsifiable concentrate). After 24 hours, aphide (Aphis fabae) were placed on the parts of the plant above the soil. The aphids were protected from contact and gas action by means of a special device. The test was carried out at 24C and 70C relative humidity. In the above test, the compounds according to Example 1 have systemic action against A phis fabae.

EXAMPLE 3 Action against Chilo suppre ssalis Six rice plants at a time of the variety Caloro were transplanted into plastic pots (diameter at the top 17 cm) and reared to a height of about 60 cm. Infestation with Chilo suppressalis larvae (L :3-4 mm long) took place 2 days after the active substance had been applied in granule form to the paddy water (rateof application: 8 kg of active substance per hectare). Evaluation of the insecticidal action took place 10 days after application of the granules. The compounds according to Example 1 were active in the above test against C h'ilo suppressalis.

EXAMPLE 4 Sterilised compost earth was homogeneously mixed with a wettable powder containing 25% of active substance so that there resulted'a rate of application of 8 kg of active substance per hectare.

Young zucchetti plants (Cucumis pepo) were put into plastic pots with the treated soil (3 plants per pot; diameter of pot 7 cm). Each pot was infected immediately afterwards with 5 Aulacophora femoralis and Pachmoda or Chortophila larvae. The control was carried out 4, 8, 16 and 32 days after depositing the larvae.

At 80100% kill after the first control, a fresh infestation with 5 larvae each was carried out in the same soil sample with 3 new zucchetti plants. If the activity was less than 80%, the remaining larvae remained in the soil sample until the control immediately following. 'If an active substance at a rate of application of 8 kg/ha still effected a 100% kill, a further control with 4 and 2 kg of active substance per hectare was carried out.

In the above test, the compounds according to Example I displayed action against Aulacophora femoralis, Pachmoda and Chortophila larvae.

EXAMPLE 5 Action against ticks A. Rhipicephalus bursa Five adult ticks'and 50 tick larvae werecounted into a glass tube and immersed for l to Z'minutes in 2' ml of an aqueous emulsion'from an emulsion. series each containing 100. 1 0. l-.or 0.1 ppm of test substance. The tube was then sealed with a standardised cotton wool plug and placed on its head, so that the active substance emulsion could be absorbed by the cotton wool.

In the case of the adults evaluation took place after 2 weeks, and in that of the larvae after 2 days. Each test was repeated twice.

B. Boophilus microplus (larvae) EXAMPLE 6 Acaricidal action Phase'olus vulgaris (drawf beans) have an infested piece of leaf from a mass culture of Telranychus urticae placed on them 12 hours before the test for the acaricidal action. The mobile stages which have migrated are sprayed with the emulsified test preparations from a chromatography atomiser so that the spray .broth does not run off. The number of living and dead larvae, adults and eggs are evaluated after 2 to 7 days under a stereoscopic microscope and the result expressed in percentages. During the *interim". the treated plants are kept in greenhouse compartments at 25C. .The compounds according to Example 1 were active in the above test against eggs, larvae and adults of Tetranychus urticae.

EXAMPLE 7 Action against soil nematodes To the test action against soil nematodes, the active substance in the concentration indicated in each case is applied to an intimately mixed with soil infected with root gall nematodes (Meloidgyne arenaria). Immediately afterwards, tomato cuttings are planted in the thus prepared soil in a series of tests and after a waiting time of 8 days tomato seeds are sown in another test series.

In order to assess the nematocidal action the galls present on the roots are counted 28 days after planting and'sowing' respectively. In this test the compounds according to Example 1 display good action against M eloidgyne arenaria.

I claim: I

l. A compound of the formula wherein R represents alkyl with l to 7 carbon atoms, Rgrepresents methyl or ethyl. R and R each repre-- sents hydrogen, nitro or halogen. m 1 to 5 and n 1 1 sulphur.

3. A compound according to claim 2, of the formula 10. A compound according to claim 2, of the formula 4. A compound according to claim 2, of the formula Br 3 7 (n) 0 I H OC2HF l l. A compound according to claim 2, of the formula v J OZIIQ Q w H (n) j 7 0 0c H 5. A compound according to claim 2, of the formula I so H (n) ll OC H Q-O-QO-K 70 12. A compound according to claim 2, of the formula 3 7 v NO I Br 9 oc u f -G 6. A compound according to claim 2, of the ormula g i v SC 3 7, (n)

s Br

u O NQ OP 2 5 13. A compoundaccording to claim 2, of the formula SC H (n) O 7. A compound according to claim 2, of the formula c1- o o P 8 SC H l (n) 1| 00 1i J O SGH( v 3 7 14. A compound according to claim 2, of the formula NO i 40 0 CO H 8; A compound according to claim 2, of the formula 0 0 g 2 5 s-cucn I 9, oc u 2 5 ClQ- 0 0 P SC 3 7 (n) 15. A compound according to claim 2, of the formula 9. A compound according to claim 2, of the formula 9 2 SC7H1 5 Disclaimer 3,927,149.0dd Kflstiomsen, Mohlin, Switzerland. O-(METHYL OR ETHYL)-O (S) LOWER ALKYL-O-(4-PHENOXYPHENYL) PHOSPHATES. Patent dated Dec. 16, 197 5. Disclaimer filed June 16, 1976, by the assignee, Cz'ba-Gez'gy Gorgaomtz'on. Hereby enters this disclaimer to claim 1 of said patent.

[Ofiicz'al Gazette August 1'7, 1976.] i" 

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1, wherein R1 represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.butyl, n-pentyl or n-heptyl, R2 represents ethyl, R3 and R4 each represents hydrogen, chlorine, bromine and/or nitro, m and n are 1 or 2, and Y represents sulphur.
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